Naphtholactam derivatives

ABSTRACT

Compounds of the formula ##STR1## where A is a heterocyclic group containing a pyridone moiety and R to R 5  are each hydrogen or substituents conventionally encountered in dyes. The compounds are eminently suitable for coloring resins and for dyeing textile materials, particularly polyester textile materials.

The present invention relates to compounds of the formula I ##STR2## where A is a radical of the formula ##STR3## n is 2 or 3, R is hydrogen or unsubstituted or substituted alkyl, cycloalkyl, aralkyl or aryl, R¹ is hydrogen, chlorine, bromine, alkyl, alkoxy, NO₂ or arylmercapto, R² is hydrogen or chlorine, R³ is hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino, alkylsulfonylamino, arylsulfonylamino, alkylmercapto, arylmercapto, arylsulfonyl, alkylsulfonyl, unsubstituted or N-substituted sulfamide, alkanoyl or aroyl, R⁴ is hydrogen, chlorine, alkoxy, arylmercapto or alkylmercapto, or R³ and R⁴ together are a radical of the formula ##STR4## R⁵ is hydrogen, chlorine or alkoxy, B is hydrogen, methyl, methoxy or chlorine, X is cyano or unsubstituted or substituted carbamoyl, Y is hydrogen, hydroxyl, alkyl of 1 to 4 carbon atoms, chlorine, bromine, C₁ to C₄ alkoxycarbonyl or unsubstituted or N-substituted carbamoyl, or X and Y together are a radical of the formula ##STR5##

More particularly, R is alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of 3 to 8 carbon atoms, β-chloroethyl, β-cyanoethyl, alkoxycarbonylethyl, where alkoxy is of 1 to 4 carbon atoms, carbamoylethyl, N-monosubstituted or N,N-disubstituted alkylcarbamoylethyl, where alkyl is of 1 to 4 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl.

Specific examples of R are propyl, butyl, hexyl, β-ethylhexyl, β-hydroxyethyl or β-hydroxypropyl, methoxyethyl, ethoxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl, amyloxypropyl, methoxycarbonylethyl, ethoxycarbonylethyl or butoxycarbonylethyl and preferably methyl, ethyl or β-cyanoethyl.

Examples of alkyl, alkoxy and arylmercapto groups R¹ are methyl, ethyl, methoxy, ethoxy and phenylmercapto which is unsubstituted or substituted by chlorine, methyl, methoxy, phenyl, phenoxy or methoxycarbonyl.

Examples of R³ are the same radicals as those mentioned for R¹, as well as naphthylmercapto, acylaminophenylmercapto, diacylaminophenylmercapto, acetylamino, propionylamino, benzoylamino which is unsubstituted by chlorine, methyl or methoxy, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, methylmercapto, ethylmercapto, β-hydroxyethylmercapto, β-hydroxypropylmercapto, butylmercapto, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl, chlorophenylsulfonyl, acetyl, chloroacetyl, propionyl, butyryl, benzoyl which is unsubstituted or substituted by methyl, methoxy, chlorine or bromine, sulfamoyl, N-methyl-, N-ethyl-, N-butyl-, N-phenyl-, N-chlorophenyl, N-methylphenyl-, N-methoxyphenyl-, N-trifluoromethylphenyl-, N-methyl-N-phenyl-, N,N-dimethyl-, N,N-diethyl-, N,N-dipropyl- and N,N-dibutyl-sulfamoyl, pyrrolidinosulfonyl, piperidinosulfonyl or morpholinosulfonyl. R³ may also be a radical of the formula NHCONH₂, NHCONHCH₃ or NHCONHC₆ H₅.

R⁴ may be hydrogen, chlorine, or one of the alkoxy, alkylmercapto and arylmercapto radicals mentioned for R¹.

Examples of alkoxy radicals R⁵ are methoxy and ethoxy. Examples of N-substituted carbamoyl radicals Y are CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₂ H₄ OH, CON(CH₃)₂, CON(C₃ H₇)₂, CON(C₄ H₉)₂ and ##STR6##

The compounds of the formula I may be manufactured by reacting compounds of the formula II ##STR7## where X¹ is oxygen or sulfur and A.sup.⊖ is an anion, and alkyl is of 1 to 4 carbon atoms, with compounds of the formula A--H₂.

If X¹ is 0, a condensing agent must be present, whilst if X¹ is S or the compounds containing the S-alkyl groups are used, this is not necessary.

Suitable condensing agents are phosphorus halides, eg. phosphorus pentachloride, phosphorus trichloride, phosphorus oxytribromide and especially phosphorus oxytrichloride.

The reaction may be carried out in an inert solvent, eg. a glycol diether or polyglycol diether, butyrolactone, toluene, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane, or in an excess of the condensing agent.

If the reaction of the naphtholactam derivatives is carried out without a condensing agent, the above solvents may again be used; additional examples of suitable solvents are pyridine, glacial acetic acid, dimethylformamide or N-methylpyrrolidone.

The compounds of the formula ##STR8## where T is oxygen and R and Y have the stated meanings, or the R bound to the ring nitrogen and T together are a radical of the formula ##STR9## and B, the other R and Y have the stated meanings, may be manufactured by reacting compounds of the formula

    Y--COCH.sub.2 COO--alkyl

with compounds of the formula ##STR10## Suitable reaction conditions are similar to those for the manufacture of, for example, 2-hydroxy-3-cyano-6-pyridones.

The reactions are known in principle. Details may be found in the Examples, in which parts and percentages are by weight.

The invention in particular relates to compounds of the formula I, where A is a radical of the formula ##STR11## n is 2 or 3, R is hydrogen, alkyl of 1 to 12 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of 3 to 8 carbon atoms, β-chloroethyl, β-cyanoethyl, alkoxycarbonylethyl, where alkoxy is of 1 to 4 carbon atoms, carbamoylethyl, N-mono- or N-di-alkylcarbamoylethyl, where alkyl is of 1 to 4 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl, R¹ is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, nitro, phenylmercapto or phenylmercapto substituted by chlorine, methyl or methoxy, R² is hydrogen or chlorine, R³ is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenoxy and nitro, alkanoylamino of 1 to 4 carbon atoms, benzoylamino, alkylsulfonylamino of 1 to 4 carbon atoms, phenylsulfonylamino, tolylsulfonylamino, alkylmercapto of 1 to 4 carbon atoms, phenylmercapto which is unsubstituted or substituted by chlorine, methyl or methoxy, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, tolylsulfonyl, sulfamoyl which is unsubstituted or is monosubstituted or disubstituted by alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of a total of 3 to 11 carbon atoms, β-cyanoethyl, β-chloroethyl, cyclohexyl, phenylalkyl (where alkyl is of 1 to 4 carbon atoms) or phenyl, sulfopiperidide, sulfopyrrolidide, sulfomorpholide, alkanoyl of 1 to 4 carbon atoms, chloroacetyl, β-chloropropionyl, or benzoyl which is unsubstituted or substituted by chlorine, methyl or methoxy, R⁴ is hydrogen, chlorine, methoxy, ethoxy, alkylmercapto of 1 to 4 carbon atoms or phenylmercapto which is unsubstituted or substituted by chlorine, methyl or methoxy, R³ and R⁴ together are a radical of the formula ##STR12## R⁵ is hydrogen, chlorine, methoxy or ethoxy, B is hydrogen, methyl, methoxy or chlorine, X is cyano, carbamoyl or CONHR, Y is hydrogen, hydroxyl, alkyl of 1 to 4 carbon atoms, chlorine, bromine, alkoxycarbonyl (where alkoxy is of 1 to 4 carbon atoms) or CONHR, or X and Y together are a radical of the formula ##STR13##

Dyes which are industrially particularly important are those of the formula I a ##STR14## where B¹ is hydrogen, alkylsulfonyl of 1 to 4 carbon atoms, allylsulfonyl, propargylsulfonyl, alkanoyl of 2 to 8 carbon atoms, benzoyl, alkylmercapto of 1 to 4 atoms or phenylmercapto, A¹ is a radical of the formula ##STR15## B² is hydrogen or methyl, and R and X have the stated meanings.

Specific examples of radicals B¹, in addition to those already mentioned, are methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonyl, acetyl, propionyl, butyryl, hexanoyl, β-ethylhexanoyl and methylmercapto, ethylmercapto, propylmercapto and butylmercapto.

X is preferably cyano.

Examples of preferred radicals R are methyl, ethyl, n-propyl and i-propyl, n-butyl and i-butyl, ω-hydroxyethyl and ω-hydroxypropyl, and ω-alkoxyethyl and ω-alkoxypropyl, where alkoxy is of 1 to 4 carbon atoms.

The compounds of the formula I may be used as dyes for textile material, especially made of polyesters, and for coloring plastics, eg. polystyrene, polycarbonate, polyolefins, polyesters, polyacrylonitrile and nylons, so as to retain their transparency.

The new dyes give brilliant hues ranging from orange to blue, which have excellent fastness to light, thermofixation and wet treatments. The fact that some of the dyes are of very high tinctorial strength should also be singled out.

EXAMPLE 1

180 parts of phosphorus oxychloride are added dropwise, at 80° C, to a mixture of 1,500 parts of ethylene glycol dimethyl ether, 169 parts of naphtholactam and 170 parts of 1-ethyl-3-cyano-6-hydroxypyrid-2-one. After a short time, a red solution forms, from which red crystals begin to separate out. The mixture is stirred for 4 hours at 80° C and 1,000 parts of methanol are added whilst the mixture is cooling. After it has cooled, the product is filtered off, washed with methanol and dried. 267 parts of a dye of the structure ##STR16## are obtained in the form of dark red crystals. When used to dye polyesters from an aqueous bath, the dye gives brilliant yellowish red hues having very good fastness properties.

Dyes with very similar hues are obtained if 1-ethyl-3-cyano-6-hydroxypyrid-2-one is replaced by the corresponding 1-propyl-, 1-butyl-, 1-(3-methoxypropyl)- or 1-(2-ethyl-hexyl)-compounds.

When 6-ethoxy-1,8-naphtholactam is condensed by a similar method with N-substituted 3-cyano-6-hydroxypyrid-2-ones, dyes which dye polyesters in neutral red hues are obtained; the dyeings are outstandingly fast.

EXAMPLE 2

276 parts of N-ethyl-4-bromonaphtholactam and 226 parts of 1-phenyl-3-cyano-4-methyl-6-hydroxypyrid-2-one are introduced into 1,000 parts of toluene and the mixture is stirred at 90° C. 165 parts of phosphorus oxychloride are added dropwise in the course of an hour and the mixture is stirred for a further 2 hours at 90° C. An equal volume of methanol is then added and the mixture is allowed to cool whilst stirring. After filtering off, washing with methanol and drying, 311 parts of a dye of the structure ##STR17## are obtained in the form of a dark crystal powder.

The dye may be used for mass-coloring polystyrene to give brilliant blue hues of good lightfastness and good heat stability.

Dyes having similar blue hues are obtained when N-ethyl-4-bromonaphtholactam is replaced by the corresponding N-butyl, N-methoxyethyl or N-cyclohexyl compounds.

EXAMPLE 3

The "naphthostyrol-imide chloride" obtained from 169 parts of naphtholactam by the method described in German Laid-Open Application DOS 1,445,624, and 209 parts of the benzimidazopyridone of the formula (B ═ H, Y ═ H) ##STR18## are introduced into 1,000 parts of nitrobenzene and the mixture is stirred at 85° C until the elimination of hydrogen chloride has ceased. After the mixture has cooled, the suspended crystals are filtered off, washed with ethanol and dried. 301 parts of a dye of the structure ##STR19## are obtained in the form of dark crystals. When used to dye polyesters from an aqueous bath, the dye gives violet dyeings which are outstandingly fast. Dyes with similar tinctorial properties are obtained if benzimidazopyridones substituted in the benz-nucleus (B ═ --CH₃, --OCH₃, --Cl, Y ═ H) are employed as the starting material. The analogous dye with Y ═ CH₃ and B ═ H is blue and may be used to color thermoplastics, giving fast blue hues.

EXAMPLE 4

385 parts of 2,4-bis-(phenylmercapto)-naphtholactam and 185 parts of 1-methyl-3-cyano-4-ethyl-6-hydroxypyrid-2-one are introduced into 1,000 parts of chlorobenzene and the mixture is stirred at 90° C. 165 parts of phosphorus oxychloride are added dropwise and stirring is continued for 1 hour at 90° C. 1,200 parts of methanol are now added to the reaction mixture, which is then left to stand for 24 hours. The product is then filtered off, washed with methanol and dried. 339 parts of a dye of the structure ##STR20## are obtained, which may be used for dyeing polyesters from an aqueous bath, and for mass-coloring polystyrene, giving pure reddish blue hues.

If 2,4-bis-(phenylmercapto)-naphtholactam is replaced by the corresponding 2,4-bis-(p-tolyl)- or 2,4-bis-(4-methoxyphenyl)- compounds, dyes giving neutral blue hues are obtained.

EXAMPLE 5

183 parts of naphtholactam-o-methyl ether and 250 parts of 1-(3-ethoxypropyl)-3-cyano-4,6-dihydroxypyrid-6-one are stirred into 1,200 parts of ethylene glycol and the mixture is heated to 125° C. It is then stirred for 8 hours at 125° - 130° C and the methanol formed is distilled off through a descending condenser. After the reaction mixture has cooled, it is filtered and the product is washed with ethanol and dried. 281 parts of a dye of the structure ##STR21## are obtained in the form of reddish brown crystals. The dye may be used for dyeing polyesters in orange red hues exhibiting a high level of fastness.

EXAMPLE 6

A mixture of 600 parts of butyrolactone, 277 parts of 4-phenylmercaptonaphtholactam and 155 parts of 1-methyl-3-cyano-6-hydroxypyrid-2-one is stirred at 80° C. 170 parts of phosphorus oxychloride are added dropwise and stirring is continued for 2 hours at 80° C. 1,000 parts of methanol are then added to the reaction mixture and the product is filtered off and rinsed with methanol. After drying, 299 parts of a dye of the structure ##STR22## are obtained in the form of brown crystals. The dye may be used for dyeing polyesters from an aqueous bath, giving vivid violet hues; the dyeings have outstanding light fastness and fastness to thermofixation. Dyes of a similar hue are obtained if the phenylmercapto-naphtholactam is replaced by the corresponding 4-tolylmercapto-, 4-methoxyphenylmercapto-, 4-chlorophenylmercapto- or 4-carbomethoxyphenylmercapto-naphtholactam.

EXAMPLE 7

271 parts of 4,5-benzoylene-naphtholactam (prepared as described in CA 53, 9183 g) and 239 parts of benzimidazopyridone of the formula ##STR23## are introduced into 1,200 parts of butyrolactone and the mixture is stirred at 120° C. 200 parts of phosphorus oxychloride are added dropwise and stirring is continued for 6 hours at 120° C. The product is filtered off at 80° C and is rinsed with warm ethanol. After drying, 399 parts of the dye of the structure ##STR24## are obtained in the form of red crystals. When worked into thermoplastics, the dye gives brilliant red hues having very good lightfastness.

EXAMPLE 8

328 parts of N-benzyl-4,5-dichloro-1,8-naphtholactam and 150 parts of 1-methyl-3-cyano-6-hydroxyoyrid-2-one are introduced into 1,200 parts of butyrolactone and the mixture is stirred at 90° C. 190 parts of phosphorus oxychloride are then added dropwise whilst stirring and the mixture is kept at 90° C for 12 hours. It is diluted with 800 parts of ethanol and the product is filtered off and washed with ethanol. After drying, 413 parts of the dye of the structure ##STR25## are obtained in the form of a dark crystal powder. The dye colors polystyrene in violet hues distinguished by very good lightfastness and heat stability. If 178 parts of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one are employed as the pyridone component, an analogous dye which may be used to color thermoplastics in blue hues is obtained.

EXAMPLE 9

307 parts of 3,4,5,6-tetrachloro-1,8-naphtholactam and 212 parts of 1-phenyl-3-cyano-6-hydroxypyrid-2-one are introduced into 1,500 parts of dehydrated nitrobenzene and the mixture is heated to 100° C. 300 parts of phosphorus oxychloride are added dropwise in the course of one hour and stirring is continued for 16 hours at 100° C. 500 parts of methanol are then added dropwise and the mixture is boiled for one hour under reflux. After filtering off, washing with methanol and drying, 443 parts of a dye of the structure ##STR26## are obtained in the form of a dark red crystal powder. When worked into thermoplastics, the dye gives red hues having excellent lightfastness.

If N-ethyl-3,4,5,6-tetrachloro-1,8-naphtholactam is used as the naphtholactam component, an analogous dye which colors thermoplastics in fast violet hues is obtained.

EXAMPLE 10

275 parts of the compound ##STR27## and 208 parts of 1-ethoxyethyl-3-cyano-6-hydroxypyrid-2-one are introduced into 2,000 parts of dichlorobenzene. The mixture is stirred at 90° C and 250 parts of phosphorus oxychloride are added in the course of 2 hours. Stirring is continued for 12 hours at 90° C and 1,000 parts of ethanol are then added carefully. The reaction mixture is boiled up briefly and is filtered warm. After washing the product with ethanol, and drying it, 398 parts of a dye of the structure ##STR28## are obtained in the form of dark crystals having a metallic gloss. When worked into polystyrene, the dye gives fast greenish blue colorations.

The further dyes shown in the Table were obtained by the processes of Examples 1 - 10.

                                      TABLE 1                                      __________________________________________________________________________     Dyes                                                                            ##STR29##                                                                     Ex-                                                                            ample                                                                              R           R.sup.3      Y       Hue                                       __________________________________________________________________________     11  (CH.sub.2).sub.3 OC.sub.5 H.sub.11                                                         Cl           CH.sub.3                                                                               violet                                    12  (CH.sub.2).sub.2 COOC.sub.3 H.sub.7                                                        H            CH.sub.3                                                                               reddish violet                            13                                                                                  ##STR30##  OC.sub.2 H.sub.5                                                                            CH.sub.3                                                                               violet                                    14  CH.sub.2 C.sub.6 H.sub.5                                                                   NHCOC.sub.2 H.sub.5                                                                         CH.sub.3                                                                               violet                                    15  CH.sub.3    SC.sub.6 H.sub.5                                                                            C.sub.2 H.sub.5                                                                        bluish violet                             16  CH.sub.2 CH.sub.2 OH                                                                       H            C.sub.4 H.sub.9                                                                        violet                                    17  C.sub.6 H.sub.5                                                                            SC.sub.4 H.sub.9                                                                            C.sub.4 H.sub.9                                                                        bluish violet                             18  H           CH.sub. 3    Br      reddish violet                            19  CH.sub.3    H            H       yellowish red                             20  C.sub.2 H.sub.5                                                                            Br           H       red                                       21  C.sub.2 H.sub.5                                                                            NO.sub.2     H       reddish violet                            22  C.sub.2 H.sub.5                                                                            OCH.sub.3    H       "                                         23  "           NHCONHCH.sub.3                                                                              H       "                                         24  "           NHSO.sub.2 C.sub.2 H.sub.5                                                                  H       "                                         25  "           SCH.sub.3    H       bluish violet                             26  "           SCH.sub.2 CHOHCH.sub.3                                                                      H       "                                         27  "           SO.sub.2 CH.sub.3                                                                           H       bluish red                                28  "           SO.sub.2 C.sub.6 H.sub.4 CH.sub.3 (4)                                                       H       "                                         29  "           COCH.sub.3   H       red                                       30  "           COCH.sub.2 Cl                                                                               H       "                                         31  "           COC.sub.6 H.sub.5                                                                           H       "                                         32  "           SO.sub.2 N(C.sub.4 H.sub.9).sub.2                                                           H       "                                         33  C.sub.3 H.sub.7 (n)                                                                        H            H       yellowish red                             34  "           CH.sub.3     H       "                                         35  C.sub.3 H.sub.7 (iso)                                                                      NHCOCH.sub.3 H       reddish violet                            36  C.sub.4 H.sub.9 (n)                                                                         NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3 (4)                                                    H       "                                         37  C.sub.4 H.sub.9 (n)                                                                        SC.sub.2 H.sub.5                                                                            H       bluish violet                             38  "           COC.sub.6 H.sub.4 CH.sub.3 (4)                                                              H       red                                       39  Ch.sub.2 CH.sub.2 OCH.sub.3                                                                H            H       yellowish red                             40  CH.sub.2 CH.sub.2 OCH.sub.3                                                                SC.sub.6 H.sub.4 CH.sub.3 (4)                                                               H       bluish violet                             41  (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                          SO.sub.2 N(CH.sub.3).sub.2                                                                  H       red                                       42  (CH.sub.2).sub.3 OC.sub.4 H.sub.9                                                          NHCOC.sub.6 H.sub.5                                                                         H       reddish violet                            43  (CH.sub.2).sub.3 OC.sub.4 H.sub.9                                                          NHCOC.sub.6 H.sub.4 OCH.sub.3 (4)                                                           H       "                                         44  CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                Br           H       red                                       45  CH.sub.2 CH.sub.2 CN                                                                        ##STR31##   H       bluish violet                             46  CH.sub.2 CH.sub.2 COOCH.sub.3                                                              NHCOC.sub.6 H.sub.4 OCH.sub.3 (4)                                                           H       reddish violet                            47  CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9                                                       H            H       yellowish red                             48  CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                      SO.sub.2 C.sub.2 H.sub.5                                                                    H       bluish red                                49  CH.sub.2 CH.sub.2 CON(CH.sub.3).sub.2                                                      SO.sub.2 C.sub.6 H.sub.4 Cl(4)                                                              H       "                                         50  CH.sub.2 CH.sub.2 CON(C.sub.4 H.sub.9).sub.2                                               H            H       yellowish red                             51  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                          H            H       "                                         52  "                                                                                           ##STR32##   H       red                                       53  C.sub.6 H.sub.5                                                                            SCH.sub.2 CH.sub.2 OH                                                                       H       bluish violet                             54  "           SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                              H       "                                         55  "           SC.sub.6 H.sub.4 Cl(4)                                                                      H       "                                         56  "           SO.sub.2 NHC.sub.4 H.sub.9                                                                  H       red                                       57  C.sub.6 H.sub.5                                                                             ##STR33##   H       "                                         58  CH.sub.3    SC.sub.6 H.sub.5                                                                            OH      bluish red                                59  C.sub.2 H.sub.5                                                                            COC.sub.2 H.sub.5                                                                           OH      reddish brown                             60  "           SO.sub.2 CH.sub.3                                                                           OH      red                                       61  "           OC.sub.2 H.sub.5                                                                            OH      reddish brown                             62  "           NHSO.sub.2 CH.sub.3                                                                         OH      "                                         63  "           SO.sub.2 N(C.sub.3 H.sub.7).sub.2                                                           OH      red                                       64  CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                         COC.sub.6 H.sub.5                                                                           OH      reddish brown                             65  (CH.sub.2).sub.3 OCH.sub.3                                                                 H            OH      orange                                    66  (CH.sub.2).sub.3 OCH.sub.3                                                                 SC.sub.6 H.sub.4 OC.sub.6 H.sub.5                                                           OH      bluish red                                67  C.sub.3 H.sub.7                                                                            H            OH      orange                                    68  "           SO.sub.2 CH.sub.3                                                                           OH      red                                       69  "           SO.sub.2 C.sub.6 H.sub.5                                                                    OH      "                                         70  CH.sub.3    H            COOCH.sub.3                                                                            violet                                    71  "           NHCONHC.sub.6 H.sub.5                                                                       COOC.sub.2 H.sub.5                                                                     bluish violet                             72  "           COC.sub.4 H.sub.9                                                                           COOC.sub.2 H.sub.5                                                                     violet                                    73  "           NHSO.sub.2 CH.sub.3                                                                         COOC.sub.2 H.sub.5                                                                     "                                         74  "           SO.sub.2 NHCH.sub.3                                                                         COOC.sub.4 H.sub.9                                                                     bluish violet                             75  "           SO.sub.2 NHC.sub.6 H.sub.4 CH.sub.3 (2)                                                     COOC.sub.4 H.sub.9                                                                     "                                         76  "            SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          CONHC.sub.2 H.sub.5                                                                    "                                         77  C.sub.2 H.sub.5                                                                            H            CONHC.sub.2 H.sub.5                                                                    violet                                    78  CH.sub.3    Cl           CON(CH.sub.3).sub.2                                                                    "                                         79  C.sub.4 H.sub.9                                                                            H            CON(CH.sub.3).sub.2                                                                    "                                         80  CH.sub.3    SC.sub.6 H.sub.5                                                                            CON(C.sub.2 H.sub.5).sub.2                                                             blue                                      81  "           COC.sub.6 H.sub.5                                                                           CON(C.sub.3 H.sub.7).sub.2                                                             violet                                    __________________________________________________________________________

                  TABLE 2                                                          ______________________________________                                         Dyes                                                                            ##STR34##                                                                     Ex.  R               R.sup.3      Y    Hue                                     ______________________________________                                         82   CH.sub.3        H            H    violet                                  83   CH.sub.3        SO.sub.2 CH.sub.3                                                                           H    bluish                                                                         violet                                  84   CH.sub.3        SC.sub.6 H.sub.5                                                                            H    blue                                    85   CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                           Cl           H    violet                                  86   CH.sub.2 CH.sub.2 CN                                                                           Br           H    "                                       87   CH.sub.2 CH.sub.2 CON(CH.sub.3).sub.2                                                          H            H    "                                       88   CH.sub.2 C.sub.6 H.sub.5                                                                       SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                             H    blue                                    89   C.sub.6 H.sub.5 SCH.sub.3    H    "                                       90   CH.sub.3        H            OH   violet                                  91   CH.sub.3        H            CH.sub.3                                                                            blue                                    92   CH.sub.3        Br           CH.sub.3                                                                            blue                                    93   "               SC.sub.6 H.sub.5                                                                            "    green-                                                                         ish                                                                            blue                                    94   "               SO.sub.2 C.sub.6 H.sub.5                                                                    "    blue                                    95   C.sub.2 H.sub.5 SCH.sub.3    "    tur-                                                                           quoise                                  96   "               SO.sub.2 CH.sub.3                                                                           "    blue                                    97   CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              COC.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                     "                                       98   CH.sub.2 CH.sub.2 COOCH.sub.3                                                                  H            C.sub.2 H.sub.5                                                                     "                                       99   "               Br           "    "                                       ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     Dyes                                                                            ##STR35##                                                                     Ex. R      R.sup.1  R.sup.3  Y    Hue                                          __________________________________________________________________________     100 CH.sub.3                                                                              SC.sub.2 H.sub.5                                                                        SC.sub.2 H.sub.5                                                                        CH.sub.3                                                                            blue                                         101 "      SC.sub.6 H.sub.4 CH.sub.3 (4)                                                           SC.sub.6 H.sub.4 CH.sub.3 (4)                                                           CH.sub.3                                                                            "                                            102 "      Cl       Cl       C.sub.2 H.sub.5                                                                     reddish                                                                        violet                                       103 "      Br       NO.sub.2 "    violet                                       104 "      SC.sub.6 H.sub.4 Cl(4)                                                                  SC.sub.6 H.sub.4 Cl(4)                                                                  "    blue                                         105 C.sub.2 H.sub.5                                                                       Br       Br       CH.sub.3                                                                            reddish                                                                        violet                                       106 "      SC.sub.6 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                        "    reddish                                                                        blue                                         107 CH.sub.3                                                                              Br       Br       H    red                                          108 "      SCH.sub.3                                                                               SCH.sub.3                                                                               H    bluish                                                                         violet                                       109 C.sub.2 H.sub.5                                                                       Br       NO.sub.2 H    bluish red                                   110 C.sub.2 H.sub.5                                                                       SC.sub.4 H.sub.9                                                                        SC.sub.4 H.sub.9                                                                        H    bluish                                                                         violet                                       111 "      SC.sub.6 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                        H    bluish                                                                         violet                                       112 "      SC.sub.6 H.sub.4 CH.sub.3 (4)                                                           NO.sub.2 H    "                                            113 C.sub.3 H.sub.7                                                                       Cl       Cl       H    red                                          114 C.sub.4 H.sub.9                                                                       SCH.sub.2 CH.sub.2 OH                                                                   SCH.sub.2 CH.sub.2 OH                                                                   H    bluish                                                                         violet                                       115 C.sub.4 H.sub.9                                                                       SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                          SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                          H    "                                            116 CH.sub.2 C.sub.6 H.sub.5                                                              Cl       Cl       H    red                                          117 CH.sub.2 C.sub.6 H.sub.5                                                              SC.sub.6 H.sub.4 Cl(4)                                                                  SC.sub.6 H.sub.4 Cl(4)                                                                  H    bluish                                                                         violet                                       118 C.sub.6 H.sub.5                                                                       SC.sub.3 H.sub.7                                                                        SC.sub.3 H.sub.7                                                                        H    "                                            119 C.sub.6 H.sub.5                                                                        SC.sub.6 H.sub.5                                                                       SC.sub.6 H.sub.5                                                                        H    "                                            120 "      SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                         SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                         H    "                                            121 "      C.sub.2 H.sub.5                                                                         H        CH.sub.3                                                                            reddish                                                                        violet                                       122 "      NO.sub.2 Br       CH.sub.3                                                                            violet                                       __________________________________________________________________________

                  TABLE 4                                                          ______________________________________                                         Dyes                                                                            ##STR36##                                                                     Ex.  R               R.sup.1 = R.sup.3                                                                       Y        Hue                                     ______________________________________                                         123  CH.sub.3        Cl       CH.sub.3 bluish                                                                         violet                                  124  "               SC.sub.6 H.sub.5                                                                        "        tur-                                                                           quoise                                  125  CH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5).sub.2                                                   Br       "        bluish                                                                         violet                                  126  C.sub.2 H.sub.5 Cl       OH       violet                                  127  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              Cl       COOCH.sub.3                                                                             blue                                    128  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              Br       "        "                                       129  CH.sub.3        Cl       H        violet                                  130  C.sub.2 H.sub.5 SC.sub.2 H.sub.5                                                                        H        blue                                    131  C.sub.2 H.sub.5 SC.sub.4 H.sub.9                                                                        H        "                                       132  C.sub.2 H.sub.5 SC.sub.6 H.sub.5                                                                        H        "                                       133  CH.sub.2 CH.sub.2 OH                                                                           Br       H        violet                                  134  (CH.sub.2).sub.3 OCH.sub.3                                                                     SCH.sub.3                                                                               H        blue                                    135  CH.sub.2 CH.sub.2 CN                                                                           "        H        "                                       136  CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7                                                           SC.sub.6 H.sub.5                                                                        H        "                                       137  CH.sub.2 CH.sub.2 CONHCH.sub.3                                                                 Cl       H        violet                                  138  CH.sub.2 CH.sub.2 CON(C.sub.3 H.sub.7).sub.2                                                   Br       H        "                                       139  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              SC.sub.3 H.sub.7                                                                        H        blue                                    ______________________________________                                    

                                      TABLE 5                                      __________________________________________________________________________     Dyes                                                                            ##STR37##                                                                     Ex-                                                                            ample                                                                              R       R.sup.3  R.sup.4  Y   Hue                                          __________________________________________________________________________     140 H       Cl       Cl       H   red                                          141 H       SCH.sub.3                                                                               SCH.sub.3                                                                               H   bluish violet                                142 CH.sub.3                                                                               Cl       Cl       H   red                                          143 C.sub.2 H.sub.5                                                                        Cl       SC.sub.6 H.sub.5                                                                        H   violet                                       144 "       Cl       SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                          H   "                                            145 "       Cl       SC.sub.6 H.sub.4 Cl(4)                                                                  H   "                                            146 "       SC.sub.2 H.sub.5                                                                        SC.sub.2 H.sub.5                                                                        H   bluish violet                                147 "       SC.sub.6 H.sub.5                                                                        H        "                                                148 CH.sub.2 CH.sub.2 OH                                                                   Cl       Cl       H   red                                          149 CH.sub.3                                                                               Cl       Cl       CH.sub.3                                                                           reddish violet                               150 CH.sub.3                                                                               SCH.sub.2 CH.sub.2 OH                                                                   SCH.sub.2 CH.sub.2 OH                                                                   "   blue                                         151 CH.sub.3                                                                               Cl       SC.sub.6 H.sub.5                                                                        "   "                                            152 CH.sub.3                                                                               H        OCH.sub.3                                                                               CH.sub.3                                                                           reddish violet                               __________________________________________________________________________

EXAMPLE 153

160 parts of phosphorus oxychloride are added dropwise at 70° C to a mixture of 800 parts of butyrolactone, 169 parts of naphtholactam and 188 parts of 1-ethyl-2-hydroxypyrid-6-one-3-carboxamide.

The mixture is stirred for 8 hours at 70° C, 400 parts of methanol and 400 parts of water are added successively and the whole is allowed to cool. After filtering off, washing and drying the product, 276 parts of the dye ##STR38## are obtained.

If the condensation is carried out at 70° C or with a substantial excess of phosphorus oxychloride, the reaction product contains substantial amounts of the dye described in Example 1. The dye of Example 153 is also obtained by hydrolyzing the dye 1, for example with 91% strength sulfuric acid at 85° C (more concentrated sulfuric acid leads to sulfonation of the naphthalene ring). The dye has very similar tinctorial properties to those of the dye described in Example 1.

                                      TABLE 6                                      __________________________________________________________________________     Dyes                                                                            ##STR39##                                                                     Ex-                                                                            ample                                                                              R.sup.1     R.sup.2                                                                          R.sup.3     R.sup.4                                                                             R.sup.5                                                                          R       Hue                               __________________________________________________________________________     154 H           H H           H    H CH.sub.3                                                                               yellowish red                     155 H           H H           H    H (CH.sub.2).sub.3 OCH.sub.3                                                             yellowish red                     156 H           H Cl          H    H C.sub.4 H.sub.9                                                                        red                               157 H           H Br          H    H C.sub.2 H.sub.5                                                                        red                               158 Br          H Br          H    H C.sub.2 H.sub.5                                                                        red                               159 H           Cl                                                                               Cl          Cl   Cl                                                                               C.sub.2 H.sub.5                                                                        red                               160 H           H SC.sub.6 H.sub.5                                                                           H    H C.sub.2 H.sub.5                                                                        violet                            161 H           H SC.sub.6 H.sub.5                                                                           SC.sub.6 H.sub.5                                                                    H C.sub.2 H.sub.5                                                                        violet                            162 H           H COC.sub.6 H.sub.5                                                                          H    H C.sub.2 H.sub.5                                                                        red                               163 H           H COCH.sub.2 CH.sub.2 Cl                                                                     H    H CH.sub.3                                                                               red                               164 H           H SO.sub.2 CH.sub.3                                                                          H    H C.sub.2 H.sub.5                                                                        bluish red                        165 H           H NO.sub.2    H    H C.sub.2 H.sub.5                                                                        reddishviolet                     166 H           H                                                                                 ##STR40##  H    H C.sub.2 H.sub.5                                                                        red                               167 H           H SO.sub.2 N(CH.sub.3).sub.2                                                                 H    H C.sub.2 H.sub.5                                                                        red                               168 SC.sub.6 H.sub.5                                                                           H SC.sub.6 H.sub.5                                                                           H    H C.sub.2 H.sub.5                                                                        bluish violet                     169                                                                                 ##STR41##  H                                                                                 ##STR42##  H    H C.sub.2 H.sub.5                                                                        bluish violet                     170 H           H SO.sub.2 N(C.sub.3 H.sub.7).sub.2                                                          H    H C.sub.2 H.sub.5                                                                        red                               171 H           H                                                                                 ##STR43##  H    H C.sub.2 H.sub.5                                                                        red                               172 H           H                                                                                 ##STR44##  H    H C.sub.2 H.sub.5                                                                        red                               173 H           H SO.sub.2 NHC.sub.6 H.sub.5                                                                 H    H C.sub.2 H.sub.5                                                                        red                               174 H           H                                                                                 ##STR45##  H    H C.sub.2 H.sub.5                                                                        red                               __________________________________________________________________________

EXAMPLE 175

200 parts of phosphorus oxychloride are added dropwise, at 80° C, to a mixture of 1,200 parts of ethylene glycol dimethyl ether, 247 parts of 4-methylsulfonyl-naphtholactam and 264 parts of N,N'-dipropyl-2-hydroxypyrid-6-one-3,4-dicarboximide. Dark crystals separate out from the solution. The mixture is boiled for 2 hours under reflux and 800 parts of methanol are added whilst it is cooling. After it has cooled, the product is filtered off, washed with methanol and dried. 401 parts of the dye having the structure ##STR46## are obtained in the form of dark crystals having a metallic gloss. The dye may be used to dye polyesters, from an aqueous bath, in brilliant neutral blue hues having good fastness properties.

                                      TABLE 7                                      __________________________________________________________________________      ##STR47##                                                                     Example                                                                             R.sup.1                                                                           R.sup.2                                                                           R.sup.3      R.sup.4                                                                           R.sup.5                                                                           R        Hue                                     __________________________________________________________________________     176  H  H  H            H  H                                                                                  ##STR48##                                                                              violet                                  177  H  H  H            H  H  CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       bluish violet                           178  Cl H  Cl           H  H  C.sub.4 H.sub.9 (iso)                                                                   reddish blue                            179  Cl H  Cl           Cl Cl CH.sub.2 CH.sub.2 CN                                                                    reddish blue                            180  H  H  Br           H  H  (CH.sub.2).sub.3 OCH.sub.3                                                              bluish violet                           181  H  H  Br           H  H                                                                                  ##STR49##                                                                              bluish violet                           182  H  H  H            H  H  C.sub.6 H.sub.5                                                                         reddish blue                            182  H  H  C.sub.2 H.sub.5 SO.sub.2                                                                    H  H  C.sub.2 H.sub.5                                                                         blue                                    183  H  H  CH.sub.3 C.sub.6 H.sub.4 SO.sub.2                                                           H  H  C.sub.4 H.sub.9                                                                         blue                                    184  H  H  CH.sub.3 CO  H  H  C.sub.5 H.sub.11                                                                        reddish blue                            185  H  H  ClCH.sub.2 CO                                                                               H  H  C.sub.3 H.sub.7 (iso)                                                                   reddish blue                            186  H  H  C.sub.2 H.sub.5 CO                                                                          H  H  C.sub.2 H.sub.5                                                                         reddish blue                            187  H  H                                                                                  ##STR50##   H  H  C.sub.2 H.sub.5                                                                         reddish blue                            188  H  H                                                                                  ##STR51##   H  H  C.sub.2 H.sub.5                                                                         reddish blue                            189  H  H                                                                                  ##STR52##   H  H  C.sub.2 H.sub.5                                                                         reddish blue                            190  H  H                                                                                  ##STR53##   H  H  C.sub.2 H.sub.4                                                                         bluish violet                           192  H  H                                                                                  ##STR54##   H  H  C.sub.2 H.sub.5                                                                         bluish violet                           193  H  H                                                                                  ##STR55##   H  H  C.sub.2 H.sub.5                                                                         bluish violet                           194  H  H                                                                                  ##STR56##   H  H  C.sub.2 H.sub.5                                                                         bluish violet                           195  H  H  CH.sub.3 NHCONH                                                                             H  H  C.sub.2 H.sub.5                                                                         bluish violet                           196  H  H  NO.sub.2     H  H  C.sub.3 H.sub.7                                                                         blue                                    __________________________________________________________________________

EXAMPLE 197

169 parts of naphtholactam and 227 parts of ##STR57## are introduced into 1,200 parts of dimethyl glycol and the mixture is stirred at 70° C. 165 parts of phosphorus oxychloride are added dropwise in the course of one hour and stirring is continued for 8 hours. After the mixture has cooled, it is filtered and the filter cake is dispersed in dilute ammonia. After again filtering off, and washing the product with water and drying it, 287 parts of the dye having the structure. ##STR58## are obtained; it may be used to dye polyesters, from an aqueous bath, in light-fast violet hues. Dyes with B ═ CH₃ or OCH₃, which have been prepared similarly, exhibit a hue somewhat shifted toward blue.

                  TABLE 8                                                          ______________________________________                                          ##STR59##                                                                     Ex.  R              R.sup.3       B     Hue                                    ______________________________________                                         198  H              Br            H     vio-                                                                           let                                    199  H              OCH.sub.3     H     blu-                                                                           ish                                                                            vio-                                                                           let                                    200  H              CH.sub.3      H     vio-                                                                           let                                    201  H              NO.sub.2      H     blu-                                                                           ish                                                                            vio-                                                                           let                                    202  H              SC.sub.6 H.sub.5                                                                             H     blue                                   203  H              SC.sub.6 H.sub.4 CH.sub.3 (4')                                                               H     blue                                   204  H              SC.sub.6 H.sub.4 OCH.sub.3 (4')                                                              H     blue                                   205  CH.sub.3       H             H     blue                                   206  CH.sub.2 CH.sub.2 CN                                                                          H             H     blue                                   207  CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                          H             H     blue                                   208  H              C1            OCH.sub.3                                                                            blue                                   209  H              H             C1    vio-                                                                           let                                    ______________________________________                                    

EXAMPLE 210

169 parts of naphtholactam and 309 parts of a compound having the structure. ##STR60## are introduced into 1,500 parts of ethylene glycol dimethyl ether, and 185 parts of phosphorus oxychloride are added at 75° C. After boiling the mixture for 4 hours, 500 parts of ethanol are added dropwise and the batch is allowed to cool. 500 parts of water are then added dropwise and the product is filtered off and washed with dilute ammonia solution and with water. After drying, 344 parts of the dye having the structure ##STR61## are obtained. This dye may be used to dye polyesters from an aqueous bath, giving slightly greenish blue dyeings with good fastness properties. Dyes of the same hue are obtained if the butyl group is replaced by other alkyl radicals, including substituted or branched radicals. Dues with B = CH₃ or OCH₃ exhibit a hue shifted somewhat more toward green.

The following are further dyes which have been prepared in accordance with the methods of Examples 1 - 10: ##STR62##

EXAMPLE 219

169 parts of naphtholactam and 210 parts of N,N'-diethyl2-hydroxypyrid-6-one-3-carboxamide are introduced into 750 parts of butyrolactone and the mixture is stirred at 70° C. 175 parts of phosphorus oxychloride are added dropwise, whereupon the reaction mixture assumes a deep red color. The mixture is stirred for a further 6 hours at 70° C, after which 250 parts of methanol and 250 parts of water are successively added dropwise. After the mixture was cooled, the crystals are filtered off and washed with 50% strength methanol. After drying, 309 parts of the dye having the structure ##STR63## are obtained in the form of a red crystal powder. The dye may be used to dye polyester fibers and fabrics, from an aqueous bath, in brilliant red hues having very good fastness properties, especially excellent light fastness.

EXAMPLE 220

277 parts of 4-phenylmercaptonaphtholactam and 182 parts of N,N'-dimethyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,000 parts of dehydrated chlorobenzene. 180 parts of phosphorus oxychloride are added dropwise at 80° C, whilst stirring, and the mixture is then kept for 4 hours at 80° C. The heating bath is then temporarily removed and 1,000 parts of methanol are carefully added to the reaction mixture. The batch is then boiled for half an hour under reflux and is allowed to cool, and the product is filtered off.

After drying, 336 parts of the dye having the structure ##STR64## are obtained in the form of a dark crystal powder. The dye may be used to dye polyesters from an aqueous bath, giving light-fast violet hues.

The pyridone derivative is obtained as follows:

72 parts of sodium methylate are introduced into a mixture of 75 parts of ethyl formate and 120 parts of ethyl acetate at -10° to 0° C, whilst stirring. The mixture is left to stand overnight at room temperature, the colorless crystal slurry is then dissolved by pouring 750 parts by volume of absolute ethanol over it, and 130 parts of malonic acid bis-methylamide are introduced. The reaction mixture is now boiled for 8 hours under reflux, in the course of which it gradually solidfies to a crystal slurry. Excess 10% strength hydrochloric acid is then added and ethanol/water is distilled off until the internal temperature has reached 100° C. On cooling, colorless crystals separate out from the clear solution; they are filtered off and dried. Yield: 123 parts of 1-methyl-2-hydroxypyrid6-one-3-carboxylic acid methylamide of melting point 206° - 208° C.

Analysis: C₈ H₁₀ N₂ O₃ (182) calculated C 52.8; H 5.5; N 15.4; O 26.4; found 52.8; 5.5; 15.5; 26.4.

                                      TABLE 9                                      __________________________________________________________________________      ##STR65##                                                                     Example                                                                             R.sup.3           A.sup.1   Hue                                           __________________________________________________________________________     221  H               CH.sub.3    red                                           222  H               C.sub.3 H.sub.7 (n)                                                                        red                                           223  H               C.sub.3 H.sub.7 (iso)                                                                      red                                           224  H               C.sub.4 H.sub.9 (n)                                                                        red                                           225  H               C.sub.4 H.sub.9 (sec)                                                                      red                                           226  H                                                                                               ##STR66##  red                                           227  H               CH.sub.2 CH.sub.2 OH                                                                       red                                           228  H               CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              red                                           229  H               CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                       red                                           230  H               CH.sub.2 CH.sub.2 CN                                                                       red                                           231  H               CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                       red                                           232  H               CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7                                                red                                           233  H               CH.sub.2 C.sub.6 H.sub.5                                                                   red                                           234  H               CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                          red                                           235  H               CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                red                                           236  H                                                                                               ##STR67##  red                                           237  H               CH.sub.2 CH(C.sub.6 H.sub.5)CH.sub.3                                                       red                                           238  H               C.sub.6 H.sub.5                                                                            red                                           239  H                                                                                               ##STR68##  red                                           240  H                                                                                               ##STR69##  red                                           241  H                                                                                               ##STR70##  bluish red                                    242  Cl              C.sub.2 H.sub.5                                                                            red                                           243  Br              C.sub.2 H.sub.5                                                                            bluish red                                    244  Br              C.sub.3 H.sub.7 (iso)                                                                      bluish red                                    245  Br              C.sub.4 H.sub.9 (n)                                                                        bluish red                                    246  CH.sub.3        CH.sub.3    red                                           247  OC.sub.2 H.sub.5                                                                               CH.sub.3    bluish red                                    248  COCH.sub.3      C.sub.2 H.sub.5                                                                            red                                           249  COCH.sub.3      C.sub.3 H.sub.7                                                                            red                                           250  COC.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                            red                                           251  COCH.sub.2 Cl   C.sub.2 H.sub.5                                                                            red                                           252  COCH.sub.2 CH.sub.2 Cl                                                                         C.sub.2 H.sub.5                                                                            red                                           253  COC.sub.6 H.sub.5                                                                              CH.sub.3    red                                           254  COC.sub.6 H.sub.5                                                                              C.sub.3 H.sub.7                                                                            red                                           255   COC.sub.6 H.sub.5                                                                             C.sub.4 H.sub.9 (sec)                                                                      red                                           256                                                                                  ##STR71##      CH.sub.3    red                                           257                                                                                  ##STR72##      CH.sub.3    red                                           258                                                                                  ##STR73##      CH.sub.3    red                                           259                                                                                  ##STR74##      CH.sub.3    red                                           260                                                                                  ##STR75##      CH.sub.3    red                                           261  SO.sub.2 CH.sub.3                                                                               CH.sub.3   bluish red                                    262  SO.sub.2 C.sub.2 H.sub.5                                                                       CH.sub.3    bluish red                                    263  SO.sub.2 CH.sub.2 CHCH.sub.2                                                                   CH.sub.3    bluish red                                    264  SO.sub.2 NHC.sub.2 H.sub.5                                                                     CH.sub.3    red                                           265  SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                   CH.sub.3    red                                           266                                                                                  ##STR76##      CH.sub.3    red                                           267  SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.4 H.sub.9                                                   C.sub.2 H.sub.5                                                                            red                                           268  SO.sub.2 N(CH.sub.3).sub.2                                                                     C.sub.4 H.sub.9 (n)                                                                        red                                           269                                                                                  ##STR77##      CH.sub.3    red                                           270  SO.sub.2 N(C.sub.4 H.sub.9).sub.2                                                              C.sub.2 H.sub.5                                                                            red                                           271  SO.sub.2 NHCl.sub.6 H.sub.5                                                                    C.sub.2 H.sub.5                                                                            red                                           272                                                                                  ##STR78##      CH.sub.3    red                                           273                                                                                  ##STR79##      C.sub.2 H.sub.5                                                                            red                                           274                                                                                  ##STR80##      C.sub.3 H.sub.7 (iso)                                                                      red                                           275  SO.sub.2 NHCH.sub.2 C.sub.6 H.sub.5                                                            C.sub.2 H.sub.5                                                                            red                                           276  SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                               CH.sub.3    red                                           277  SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.3).sub.2 OC.sub.6 H.sub.5                                  CH.sub.3   red                                           278                                                                                  ##STR81##      C.sub.4 H.sub.9                                                                            red                                           279                                                                                  ##STR82##      C.sub.4 H.sub.9 (tertiary)                                                                 red                                           280                                                                                  ##STR83##      C.sub.3 H.sub.7 (n)                                                                        red                                           281                                                                                  ##STR84##      C.sub.2 H.sub.5                                                                            red                                           282  SC.sub.2 H.sub.5                                                                               CH.sub.3    violet                                        283  SCH.sub.2 CH.sub.2 OH                                                                          CH.sub.3    violet                                        284  SC.sub.4 H.sub.9                                                                               C.sub.2 H.sub.5                                                                            violet                                        285  SC.sub.6 H.sub.5                                                                               C.sub.2 H.sub.5                                                                            violet                                        286  SC.sub.6 H.sub.5                                                                               C.sub.3 H.sub.7 (iso)                                                                      violet                                        287                                                                                  ##STR85##      CH.sub.3    violet                                        288                                                                                  ##STR86##      CH.sub.3    violet                                        289                                                                                  ##STR87##      CH.sub.3    violet                                        290                                                                                  ##STR88##      CH.sub.3    violet                                        291                                                                                  ##STR89##      CH.sub.3    violet                                        292                                                                                  ##STR90##      C.sub.2 H.sub.5                                                                            violet                                        293                                                                                  ##STR91##      CH.sub.3    violet                                        294                                                                                  ##STR92##      CH.sub.3    violet                                        295  SO.sub.2 C.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                            bluish red                                    296                                                                                  ##STR93##      C.sub.2 H.sub.5                                                                            bluish red                                    297  NO.sub.2        CH.sub.3    bluish red                                    298  NO.sub.2        C.sub.2 H.sub.5                                                                            bluish red                                    299  NO.sub.2        C.sub.3 H.sub.7                                                                            bluish red                                    300  NO.sub.2        C.sub.3 H.sub.7 (iso)                                                                      bluish red                                    301  NHCOCH.sub.3    C.sub.2 H.sub.5                                                                            reddish violet                                302  NHCOC.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            reddish violet                                303  NHCONH.sub.2    C.sub.2 H.sub.5                                                                            reddish violet                                304  NHCOC.sub.6 H.sub.5                                                                            C.sub.3 H.sub.7                                                                            reddish violet                                305  NHSO.sub.2 CH.sub.3                                                                            C.sub.2 H.sub. 5                                                                           reddish violet                                306  NHSO.sub.2 C.sub.4 H.sub.9                                                                     CH.sub.3    reddish violet                                307                                                                                  ##STR94##      C.sub.2 H.sub.5                                                                            reddish violet                                308                                                                                  ##STR95##      C.sub.2 H.sub.5                                                                            reddish violet                                __________________________________________________________________________

EXAMPLE 309

190 parts of phosphorus oxychloride are added in the course of one hour to a mixture of 1,200 parts of butyrolactone, 259 parts of N-benzyl-naphtholactam and 266 parts of N,N'-dibutyl-2-hydroxypyrid6-one-3-carboxamide at 100° C and the batch is kept at this temperature for 2 hours. The heating is then discontinued and 800 parts of methanol are added dropwise at a rate such that the reaction mixture comes to the boil. In the course thereof, the dark melt turns to a crystal suspension, which is filtered after it has cooled. After washing the product with methanol and drying, 355 parts of the dye having the structure ##STR96## are obtained. When worked into thermoplastics, the dye gives violet hues having very good lightfastness. Tinctorially equivalent dyes are obtained with N-phenylnaphtholactam and N-phenylethylnaphtholactam.

                                      TABLE 10                                     __________________________________________________________________________     Dyes                                                                            ##STR97##                                                                     Example                                                                              R           R.sup.3  A   A.sup.1                                                                             Hue                                        __________________________________________________________________________     310   CH.sub.3    H        H   C.sub.2 H.sub.5                                                                     violet                                     311   CH.sub.3    H        CH.sub.3                                                                           CH.sub.3                                                                            blue                                       312   C.sub.2 H.sub.5                                                                            Br       H   CH.sub.3                                                                            violet                                     313   CH.sub.3    H        C.sub.4 H.sub.9                                                                    CH.sub.3                                                                            blue                                       314   H           COC.sub.6 H.sub.5                                                                       CH.sub.3                                                                           CH.sub.3                                                                            reddish violet                             315   H           H        OH  C.sub.2 H.sub.5                                                                     orange                                     316   H           SO.sub.2 CH.sub.3                                                                       OH  C.sub.3 H.sub.7                                                                     yellowish red                              317   H           SC.sub.6 H.sub.5                                                                        OH  CH.sub.3                                                                            dull bluish                                                                    red                                        318   H           SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       OH  C.sub.2 H.sub.5                                                                     yellowish red                              319   CH.sub.2 CH.sub.2 CN                                                                       H        OH  CH.sub.3                                                                            violet                                     320   C.sub.4 H.sub.9                                                                            COC.sub.6 H.sub.5                                                                       OH  C.sub.2 H.sub.5                                                                     violet                                     321   C.sub.2 H.sub.5                                                                            SC.sub.6 H.sub.5                                                                        OH  CH.sub.3                                                                            reddish blue                               322   CH.sub.2 C.sub.6 H.sub.5                                                                   H        OH  C.sub.4 H.sub.9                                                                     violet                                     323   (CH.sub.2).sub.2 COOCH.sub.3                                                               Cl       H   C.sub.2 H.sub.5                                                                     violet                                     324   (CH.sub.2).sub.2 CON(CH.sub.3).sub.2                                                       H        H   CH.sub.3                                                                            violet                                     325   CH.sub.3    SC.sub.6 H.sub.5                                                                        H   CH.sub.3                                                                            reddish blue                               326   (CH.sub.2).sub.3 OCH.sub.3                                                                 Br       H   CH.sub.3                                                                            violet                                     __________________________________________________________________________

                                      TABLE 11                                     __________________________________________________________________________     Dyes                                                                            ##STR98##                                                                     Example                                                                              R.sup.1     R.sup.3   A   A.sup.1                                                                             Hue                                       __________________________________________________________________________     327   Cl          Cl        H   C.sub.2 H.sub.5                                                                     red                                       328   Cl          NO.sub.2  H   C.sub.2 H.sub.5                                                                     red                                       329   Br          Br        H   C.sub.3 H.sub.7                                                                     bluish red                                330   Br          NO.sub.2  H   CH.sub.3                                                                            bluish red                                331   NO.sub.2    Br        H   C.sub.2 H.sub.5                                                                     red                                       332   SCH.sub.3   SCH.sub.3 H   C.sub.2 H.sub.5                                                                     bluish violet                             333   SCH.sub.2 CH.sub.2 OH                                                                      SCH.sub.2 CH.sub.2 OH                                                                    H   CH.sub.3                                                                            bluish violet                             334   SC.sub.6 H.sub.5                                                                           SC.sub.6 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                     bluish violet                             335                                                                                   ##STR99##                                                                                  ##STR100##                                                                              H   CH.sub.3                                                                            violet                                    336                                                                                   ##STR101##                                                                                 ##STR102##                                                                              H   C.sub.2 H.sub.5                                                                     bluish violet                             337   Br          Br        OH  C.sub.2 H.sub.5                                                                     reddish orange                            338   SC.sub.6 H.sub.5                                                                           SC.sub.6 H.sub.5                                                                         OH  CH.sub.3                                                                            violet                                    339                                                                                   ##STR103##                                                                                 ##STR104##                                                                              OH  C.sub.2 H.sub.5                                                                     violet                                    340   Cl          Cl        CH.sub.3                                                                           CH.sub.3                                                                            reddish violet                            341   SC.sub.6 H.sub.5                                                                           SC.sub.6 H.sub.5                                                                         CH.sub.3                                                                           CH.sub.3                                                                            blue                                      __________________________________________________________________________

                                      TABLE 12                                     __________________________________________________________________________     Dyes                                                                            ##STR105##                                                                    Example                                                                              R.sup.3     R.sup.4   A   A.sup.1                                                                             Hue                                       __________________________________________________________________________     342    Cl         Cl        H   C.sub.2 H.sub.5                                                                     red                                       343   Cl          Cl        H   C.sub.3 H.sub.7                                                                (iso)                                                                               red                                       344   SC.sub.2 H.sub.5                                                                           SC.sub.2 H.sub.5                                                                         H   CH.sub.3                                                                            bluish violet                             345   Cl          SC.sub.6 H.sub.5                                                                         H   C.sub.2 H.sub.5                                                                     reddish violet                            346   Cl          SC.sub.6 H.sub.5                                                                         H   C.sub.4 H.sub.9                                                                     reddish violet                            347   Cl                                                                                          ##STR106##                                                                              H   C.sub.2 H.sub.5                                                                     reddish violet                            348   Cl                                                                                          ##STR107##                                                                              H   C.sub.2 H.sub.5                                                                     reddish violet                            349   H            OCH.sub.3                                                                               H   CH.sub.3                                                                            red                                       350   Cl          Cl        OH  C.sub.2 H.sub.5                                                                     orange                                    351   Cl                                                                                          ##STR108##                                                                              OH  C.sub.2 H.sub.5                                                                     red                                       352   SC.sub.6 H.sub.5                                                                           SC.sub.6 H.sub.5                                                                         OH  C.sub.2 H.sub.5                                                                     reddish violet                            353   Cl          Cl        CH.sub.3                                                                           CH.sub.3                                                                            reddish violet                            354   SCH.sub.3   SCH.sub.3 CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     blue                                      355                                                                                   ##STR109##                                                                                 ##STR110##                                                                              CH.sub.3                                                                           CH.sub.3                                                                            blue                                      __________________________________________________________________________

EXAMPLE 356

307 parts of 3,4,5,6-tetrachloronaphtholactam and 250 parts of N,N'-diisopropyl-2-hydroxypyrid-6-one are introduced into 1,300 parts of dehydrated nitrobenzene and the mixture is stirred at 90° C. 195 parts of phosphorus oxychloride are added dropwise and stirring is continued for 4 hours at 99° - 100° C. The excess phosphorus oxychloride is then decomposed by adding 700 parts of ethanol and the mixture is boiled up briefly and allowed to cool. After filtering off, washing the product with ethanol and drying it, 411 parts of the dye having the structure ##STR111## are obtained. In polystyrene, this dye gives heat-stable and very light-fast brilliant red colorations. The dye with R ═ H and A ═ OH, prepared similarly, colors polystyrene reddish orange whilst the dye with R ═ --CH₃ and A ═ H colors polystyrene violet.

EXAMPLE 357

271 parts of 4,5-benzoylenenaphtholactam (prepared as described in C.A. 53, 9183 g) and 300 parts of N,N'-bis-methoxypropyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,200 parts of dehydrated dichlorobenzene and the mixture is stirred at 100° C. 200 parts of phosphorus oxychloride was added dropwise and stirring is continued for 4 hours at 110° C. When the mixture has cooled, 800 parts of methanol are added and the product is filtered off and washed with methanol. After it has been dried, 443 parts of the dye of the formula ##STR112## are obtained. When worked into thermoplastics, the dye gives reddish violet colorations distinguished by very good lightfastness.

EXAMPLE 358

275 parts of the compound ##STR113## and 266 parts of N,N'-bis-isobutyl-2-hydroxypyrid-6-one-3-carboxamide are introduced into 1,500 parts of butyrolactone. The mixture is stirred at 90° C and 200 parts of phosphorus oxychloride are added in the course of 2 hours. Stirring is continued for 10 hours at 90° C and 1,000 parts of methanol are then added dropwise, whilst discontinuing the heating. After filtering off, washing the product with methanol and drying it, 336 parts of the dye having the structure ##STR114## are obtained. This dye, worked into polystyrene or other thermoplastics, gives light-fast greenish blue colorations.

EXAMPLE 359

250 parts of phosphorus oxychloride are added in the course of 2 hours to a mixture of 1,400 parts of ethylene glycol dimethyl ether, 169 parts of naphtholactam and 299 parts of the compound ##STR115## whilst stirring at 70° C. The mixture is then stirred for a further 6 hours at 70° C, after which 1,000 parts of methanol are added. When the mixture has cooled, it is filtered and the filter residue is dispersed in dilute ammonia. After again filtering off, washing the product with water and drying it, 297 parts of the dye ##STR116## are obtained. This dye may be used to dye polyester fibers and fabrics from an aqueous bath, giving strong brilliant violet dyeings distinguished by good lightfastness and fastness to thermofixation. Dyes with equivalent tinctorial properties are obtained by varying A¹ from methyl to 2-ethylhexyl, the optimum affinity being found with a total of from 4 to 5 carbon atoms.

The condensation products may be prepared by, for example, the following method:

77 parts of sodium methylate are introduced into a mixture of 80 parts of ethyl formate and 140 parts of ethyl acetate whilst cooling at from -20° to 0° C. After being left to stand overnight, the colorless slurry of the sodium salt of formylethyl acetate is dissolved by adding 400 parts by volume of ethylene glycol monomethyl ether, and 189 parts of benzimidazolyl-2-aceto-N-methylamide are added to the solution. The mixture is boiled for 4 hours under reflux, 600 parts by volume of water are added and the batch is acidified with concentrated hydrochloric acid. The reaction mixture is boiled for 1/2 hour, sodium acetate is added until the mixture reacts neutral, and the product is filtered off. After washing the product with warm water and drying it, 208 parts of the compound of the formula ##STR117## are obtained. The melting point of a sample recrystallized from dimethylformamide is 321° C (with decomposition).

Analysis: C₁₃ H₁₁ N₃ O₂ (241); calculated C 64.8 H 4.6 N 17.4 O 13.3; found 64.5 4.9 17.3 13.7.

                                      TABLE 13                                     __________________________________________________________________________     Dyes                                                                            ##STR118##                                                                    Example                                                                             R       R.sup.3     A     A.sup.1 Y        Hue                            __________________________________________________________________________     360  C.sub.2 H.sub.5                                                                        H           H     C.sub.4 H.sub.9                                                                        H        blue                           361  H       Br          H     C.sub.2 H.sub.5                                                                        H        violet                         362  H       SO.sub.2 CH.sub.3                                                                          H     (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                      H        bluish                                                                         violet                         363  H       H           H     C.sub.3 H.sub.7                                                                        Cl       violet                         364  H       H           H     C.sub.3 H.sub.7                                                                        CH.sub.3 violet                         365  H       Cl          H     (CH.sub.2).sub.3 OCH.sub.3                                                             OCH.sub.3                                                                               bluish                                                                         violet                         366  H       NO.sub.2    H     (CH.sub.2).sub.3 OCH.sub.3                                                             H        blue                           367  H       SC.sub.6 H.sub.5                                                                           H     C.sub.4 H.sub.9                                                                        H        blue                           368  H       SO.sub.2 N(C.sub.4 H.sub.9).sub.2                                                          H     CH.sub.3                                                                               H        bluish                                                                         violet                         369  H                                                                                       ##STR119## H     C.sub.2 H.sub.5                                                                        H        bluish violet                  370  H       COC.sub.2 H.sub.5                                                                          H     C.sub.4 H.sub.9                                                                        H        bluish                                                                         violet                         371  H       H           CH.sub.3                                                                             CH.sub.3                                                                               H        blue                           372  H       Br          CH.sub.3                                                                             CH.sub.3                                                                               H        blue                           373  H       H           OH    C.sub.2 H.sub.5                                                                        H        reddish                                                                        violet                         374  CH.sub.3                                                                               H           OH    CH.sub.3                                                                               H        bluish                                                                         violet                         375  CH.sub.2 CH.sub.2 CN                                                                   Br          H     CH.sub.3                                                                               H        blue                           376  CH.sub.2 C.sub.6 H.sub.5                                                               H           H     CH.sub.3                                                                               H        blue                           377  H       H           H     C.sub.3 H.sub.7                                                                        CON(CH.sub.3).sub.2                                                                     bluish                                                                         violet                         378  H       Cl          H     C.sub.2 H.sub.5                                                                        CON(C.sub.4 H.sub.9).sub.2                                                              bluish                                                                         violet                         379  H       H           H     C.sub.2 H.sub.5                                                                        COOCH.sub. 3                                                                            bluish                                                                         violet                         __________________________________________________________________________ 

I claim:
 1. A compound of the formula ##STR120## n is 2, R is hydrogen, alkyl of 1 to 12 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of 3 to 8 carbon atoms, β-chloroethyl, β-cyanoethyl, C₁ to C₄ alkoxycarbonylethyl, carbamoylethyl, N-mono- or N-di-alkylcarbamoylethyl, where alkyl is of 1 to 4 carbon atoms, cyclohexyl, benzyl, phenylethyl or phenyl, R¹ is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, nitro and phenylmercapto, or phenylmercapto substituted by chlorine, methyl or methoxy, R² is hydrogen or chlorine, R³ is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, phenoxy and nitro, alkanoylamino of 1 to 4 carbon atoms, benzoylamino, alkylsulfonylamino of 1 to 4 carbon atoms, phenylsulfonylamino, tolylsulfonylamino, alkylmercapto of 1 to 4 carbon atoms, phenylmercapto or phenylmercapto substituted by chlorine, methyl or methoxy, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, tolylsulfonyl, sulfamoyl which is unsubstituted or is monosubstituted or disubstituted by alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of a total of 3 to 11 carbon atoms, β-cyanoethyl, β-chloroethyl, cyclohexyl, phenylalkyl (where alkyl is of 1 to 4 carbon atoms) or phenyl, sulfopiperidide, sulfopyrrolidide, sulfomorpholide, alkanoyl of 1 to 4 carbon atoms, chloroacetyl, β-chloropropionyl, benzoyl or benzoyl substituted by chlorine, methyl or methoxy, R⁴ is hydrogen, chlorine, methoxy, ethoxy, alkylmercapto of 1 to 4 carbon atoms or phenylmercapto or phenylmercapto substituted by chlorine, methyl or methoxy, R³ and R⁴ together are ##STR121## R⁵ is hydrogen, chlorine, methoxy or ethoxy, B is hydrogen, methyl, methoxy or chlorine, X is cyano, carbamoyl or CONHR, Y is hydrogen, hydroxyl, alkyl of 1 to 4 carbon atoms, chlorine, bromine, C₁ to C₄ alkoxycarbonyl or CONHR, or X and Y together are ##STR122## and Z is >N-R.
 2. A compound as claimed in claim 1, where R², R⁴ and R⁵ are hydrogen.
 3. A compound as claimed in claim 1, where R¹ is hydrogen, chlorine or bromine.
 4. A compound as claimed in claim 1, where R³ is hydrogen, chlorine, bromine, methoxy, ethoxy, phenylmercapto, benzoyl, phenylmercapto or benzoyl substituted by chlorine, methyl or methoxy, methylsulfonyl, acetyl, propionyl or sulfamoyl which is monosubstituted or disubstituted by alkyl of 4 to 8 carbon atoms.
 5. A compound as claimed in claim 1, where R is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of a total of 3 to 8 carbon atoms, or β-cyanoethyl.
 6. A compound as claimed in claim 1, where A is ##STR123## B is hydrogen, chlorine, methyl or methoxy, R is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms, alkoxyalkyl of a total of 3 to 8 carbon atoms or β-cyanoethyl, X is cyano, carbamoyl or CONHR, and Y is hydrogen, or X and Y together are ##STR124##
 7. A compound as claimed in claim 1, of the formula ##STR125## where R³ is hydrogen, chlorine, bromine, methoxy, ethoxy, phenylmercapto, benzoyl, phenylmercapto or benzoyl substituted by chlorine, methyl or methoxy, methylsulfonyl, acetyl, propionyl or sulfamoyl which is monosubstituted or disubstituted by alkyl of 4 to 8 carbon atoms, and A is ##STR126## and R and B have the meanings given in claim
 6. 8. A compound as claimed in claim 1, of the formula ##STR127## where alkyl is of 2 to 4 carbon atoms.
 9. A compound as claimed in claim 1, of the formula ##STR128## where alkyl is of 3 to 8 carbon atoms or is hydroxyalkyl or alkoxyalkyl of a total of 2 to 8 carbon atoms and B has the stated meanings.
 10. A compound as claimed in claim 1 wherein A is ##STR129## wherein X, Y and R have the stated meanings.
 11. A compound as claimed in claim 1 wherein A is ##STR130## wherein X, Y and n have the stated meanings.
 12. A compound as claimed in claim 1 wherein A is ##STR131## wherein X, Z and B have the stated meanings.
 13. A compound as claimed in claim 1 wherein A is ##STR132## wherein X, Y and B have the stated meanings. 